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• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
  • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
  • C08L23/10—Homopolymers or copolymers of propene
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B27/00—Layered products comprising a layer of synthetic resin
  • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
  • B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B27/00—Layered products comprising a layer of synthetic resin
  • B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
  • C08J5/18—Manufacture of films or sheets
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
  • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
  • C08L23/18—Homopolymers or copolymers of hydrocarbons having four or more carbon atoms
  • C08L23/20—Homopolymers or copolymers of hydrocarbons having four or more carbon atoms having four to nine carbon atoms
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
  • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
  • C08L23/18—Homopolymers or copolymers of hydrocarbons having four or more carbon atoms
  • C08L23/20—Homopolymers or copolymers of hydrocarbons having four or more carbon atoms having four to nine carbon atoms
  • C08L23/22—Copolymers of isobutene; Butyl rubber ; Homo- or copolymers of other iso-olefins
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B2270/00—Resin or rubber layer containing a blend of at least two different polymers
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B2307/00—Properties of the layers or laminate
  • B32B2307/30—Properties of the layers or laminate having particular thermal properties
  • B32B2307/31—Heat sealable
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B2307/00—Properties of the layers or laminate
  • B32B2307/40—Properties of the layers or laminate having particular optical properties
  • B32B2307/412—Transparent
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B2307/00—Properties of the layers or laminate
  • B32B2307/50—Properties of the layers or laminate having particular mechanical properties
  • B32B2307/514—Oriented
  • B32B2307/518—Oriented bi-axially
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B2307/00—Properties of the layers or laminate
  • B32B2307/50—Properties of the layers or laminate having particular mechanical properties
  • B32B2307/54—Yield strength; Tensile strength
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B2307/00—Properties of the layers or laminate
  • B32B2307/70—Other properties
  • B32B2307/724—Permeability to gases, adsorption
  • B32B2307/7242—Non-permeable
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B2307/00—Properties of the layers or laminate
  • B32B2307/70—Other properties
  • B32B2307/724—Permeability to gases, adsorption
  • B32B2307/7242—Non-permeable
  • B32B2307/7244—Oxygen barrier
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B2307/00—Properties of the layers or laminate
  • B32B2307/70—Other properties
  • B32B2307/724—Permeability to gases, adsorption
  • B32B2307/7242—Non-permeable
  • B32B2307/7246—Water vapor barrier
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B2307/00—Properties of the layers or laminate
  • B32B2307/70—Other properties
  • B32B2307/75—Printability
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B2439/00—Containers; Receptacles
  • B32B2439/40—Closed containers
  • B32B2439/46—Bags
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B2439/00—Containers; Receptacles
  • B32B2439/70—Food packaging
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
  • C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
  • C08J2323/10—Homopolymers or copolymers of propene
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
  • C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
  • C08J2323/10—Homopolymers or copolymers of propene
  • C08J2323/12—Polypropene
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
  • C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
  • C08J2323/18—Homopolymers or copolymers of hydrocarbons having four or more carbon atoms
  • C08J2323/20—Homopolymers or copolymers of hydrocarbons having four or more carbon atoms having four to nine carbon atoms

Definitions

• the present invention relates to polyolef ⁇ n compositions and films obtained from the said compositions, especially suitable for the packaging of fresh foodstuff, like salad and vegetables.
• polypropylene films and particularly biaxially oriented polypropylene films (BOPP) , are widely used for the packaging of foodstuff using automatic machines.
• the said films are characterized by a particular good balance of processability ("machinability"), optical and mechanical properties, and low permeability to gases, in particular oxygen and carbon dioxide, and water vapour.
• Films suitable for packaging fresh produce items that continue to respire after they are harvested are described in US6410136, US6485817 and US6514625.
• the films therein described are obtained combining ethylene/propylene, butene/propylene copolymers or ethylene/propylene/butene terpolymers, with polypropylene.
• OTR oxygen transmission rate
• WVTR water vapour transmission rate
• the films are characterized by a very high balance of Tensile Strength and Haze (of less than 2%) in addition to the said permeability, and are particularly suited for the packaging of fresh foodstuff, like salad and vegetables.
• component (A) of the composition of the present invention are preferably selected from ethylene, propylene and C5-C8 alpha- olef ⁇ ns, such as for example 1-pentene, 1-hexene, 1-octene, 4-methyl-l-pentene.
• component (B) of the composition of the present invention are preferably selected from ethylene and C4-C8 alpha-olefins, such as for example 1-butene.
• compositions of the present invention are: amount of copolymer fraction (i): from 30% to 90%, more preferably from 50% to 75% by weight, with respect to the weight of (A); amount of ethylene in the copolymer fraction (i): from 6.2% to 20%, more preferably from 6.5% to 20%, in particular from 6.5 to 15% by weight with respect to the weight of (i);
• melt flow rate (MFR according to ASTM D 1238, condition L) of the overall composition from 0.1 to 20, more preferably from 1 to 5 g/10 min;
• the butene-1 polymers (A) of the compositions of the present invention can be prepared by polymerization of the monomers in the presence of a stereospecif ⁇ c catalyst comprising (i) a solid component comprising a Ti compound and an internal electron-donor compound supported on MgCl 2 ; (ii) an alkylaluminum compound and, optionally, (iii) an external electron-donor compound.
• a stereospecif ⁇ c catalyst comprising (i) a solid component comprising a Ti compound and an internal electron-donor compound supported on MgCl 2 ; (ii) an alkylaluminum compound and, optionally, (iii) an external electron-donor compound.
• Magnesium dichloride in active form is preferably used as a support. It is widely known from the patent literature that magnesium dichloride in active form is particularly suited as a support for Ziegler-Natta catalysts. In particular, USP 4,298,718 and USP 4,495,338 were the first to describe the use of these compounds in Ziegler-Natta catalysis.
• magnesium dihalides in active form used as support or co- support in components of catalysts for the polymerization of olefins are characterized by X-ray spectra in which the most intense diffraction line that appears in the spectrum of the non-active halide is diminished in intensity and is replaced by a halo whose maximum intensity is displaced towards lower angles relative to that of the more intense line.
• the preferred titanium compounds used in the catalyst component of the present invention are TiCl 4 and TiCl 3 ; furthermore, also Ti-haloalcoholates of formula Ti(OR) n- y X y , where n is the valence of titanium, X is halogen, preferably chlorine, and y is a number between 1 and n, can be used.
• the internal electron-donor compound is preferably selected from esters and more preferably from alkyl, cycloalkyl or aryl esters of monocarboxylic acids, for example benzoic acids, or polycarboxylic acids, for example phthalic or succinic acids, the said alkyl, cycloalkyl or aryl groups having from 1 to 18 carbon atoms.
• Examples of the said electron-donor compounds are diisobutyl phthalate, diethylphtahalate and dihexylphthalate.
• the internal electron donor compound is used in molar ratio with respect to the MgCl 2 of from 0.01 to 1 preferably from 0.05 to 0.5.
• the alkyl-Al compound (ii) is preferably chosen among the trialkyl aluminum compounds such as for example triethylaluminum, triisobutylaluminum, tri-n- butylaluminum, tri-n-hexylaluminum, tri-n-octylaluminum. It is also possible to use mixtures of trialkylaluminum compounds with alkylaluminum halides, alkylaluminum hydrides or alkylaluminum sesquichlorides such as AlEt 2 Cl and Al 2 Et 3 CIa .
• the external donors (iii) are preferably selected among silicon compounds of formula R a 1 R b 2 Si(OR 3 ) c , where a and b are integer from 0 to 2, c is an integer from 1 to 3 and the sum (a+b+c) is 4; R 1 , R 2 , and R 3 , are alkyl, cycloalkyl or aryl radicals with 1-18 carbon atoms optionally containing heteroatoms.
• a particularly preferred group of silicon compounds is that in which a is 0, c is 3, b is 1 and R 2 is a branched alkyl or cycloalkyl group, optionally containing heteroatoms, and R 3 is methyl.
• Examples of such preferred silicon compounds are cyclohexyltrimethoxysilane, t-butyltrimethoxysilane and thexyltrimethoxysilane.
• the use of thexyltrimethoxysilane is particularly preferred.
• the electron donor compound (iii) is used in such an amount to give a molar ratio between the organoaluminum compound and said electron donor compound (iii) of from 0.1 to 500, preferably from 1 to 300 and more preferably from 3 to 100.
• the catalyst In order to make the catalyst particularly suitable for the polymerization step, it is possible to pre-polymerize said catalyst in a pre-polymerization step.
• Said prepolymerization can be carried out in liquid, (slurry or solution) or in the gas-phase, at temperatures generally lower than 100 0 C, preferably between 20 and 70 0 C.
• the prepolymerization step is carried out with small quantities of monomers for the time which is necessary to obtain the polymer in amounts of between 0.5 and 200Og per g of solid catalyst component, preferably between 5 and 500 and, more preferably, between 10 and lOOg per g of solid catalyst component.
• the polymerization process can be carried out according to known techniques, for example slurry polymerization using as diluent a liquid inert hydrocarbon, or solution polymerization using for example the liquid butene-1 as a reaction medium. Moreover, it may also be possible to carry out the polymerization process in the gas-phase, operating in one or more fluidized or mechanically agitated bed reactors. The polymerization carried out in the liquid butene-1 as a reaction medium is highly preferred.
• a preferred method of preparing a polymer composition (A) containing ethylene only consists of carrying out the polymerization in at least two sequential stages (as illustrated in the following examples), the copolymer fraction (i) being prepared in one of such stages.
• the propylene polymers (B) of the compositions of the present invention can be prepared by polymerization of the monomers in the presence of a stereospecific catalyst of the same kind as described above for (A), using well known polymerization techniques in liquid phase (solution or liquid monomer) or in gas phase.
• the films of the present invention can be mono-layer films, but preferably they are multilayer, and comprise at least one layer composed of or comprising the polyolef ⁇ n composition of the present invention.
• the films of the present invention can have a Y, X/Y or a X/Y/X structure, wherein Y is the layer composed of or comprising the polyolefin composition of the present invention.
• the X layer(s), equal or different, preferably are composed of or comprise polyolefin materials selected from the above described propylene polymers (B) of the compositions of the present invention, or olefin polymers or polymer compositions having heat-seal properties and/or good compatibility with inks (printability).
• the said olefin polymers or polymer compositions are preferably selected from copolymers of propylene with one or more comonomers selected from ethylene and C4-C8 alpha-olefins, preferably butene-1, or combinations of said copolymers.
• the said comonomers are present in amounts up to 40% by weight.
• the said layers may also contain the additives that are commonly used for the film manufacturing, and especially for the films used for packaging applications with automatic machines, such as anti-oxydants, process stabilizers, slip agents, antistatic agents, antiblock agents.
• the films of the present invention are at least monoaxially oriented, more preferably they are bioriented films (BOPP).
• BOPP bioriented films
• the overall film thickness is preferably from 9 to 100 microns
• the thickness of the skin layer(s) X is preferably from 0.5 to 3 microns
• that of the layer(s) Y, typically used as inner layer(s) is from 9.5 to 100 microns.
• the said films are produced by using processes well known in the art.
• extrusion processes can be used.
• the polymer materials to be used for the various layers are molten in different extruders and extruded through a narrow die slit. Subsequent from the exit from the die, the material can be cooled, heated and oriented in several ways or in combination to produce a that stated thin film. Examples of such common to the polymer processing industry are cast, blown, extrusion coating, uniaxially oriented, simultaneous biaxially oriented, and sequential biaxially oriented film processes.
• the extruded molten material is pulled away from the slit and cooled before winding- up.
• extrusion processes are the blown film and BOPP processes hereinbelow explained.
• the molten polymer materials are forced through a circular shaped slit.
• the extrudate which is drawn off has the shape of a tube, which is inflated by air to form a tubular bubble.
• the bubble is cooled and collapsed before winding-up.
• the molten polymer materials are forced continuously through a narrow slit.
• the extruded molten material is pulled away from the slit and cooled, then heated again and stretched both in the Machine Direction (MD) and in the Transverse Direction (TD). After the stretching process, the film is cooled and then wound-up.
• MD Machine Direction
• TD Transverse Direction
• 13 C-NMR spectra are performed on a polymer solution (8-12 %wt) in dideuterated 1,1,2,2-tetrachloro-ethane at 120 0 C.
• the 13 C NMR spectra are acquired on a Bruker DPX- 400 spectrometer operating at 100.61 MHz in the Fourier transform mode at 120 0 C using a 90° pulse, 15 seconds of delay between pulses and CPD (WALTZ16) to remove 1 H- 13 C coupling.
• About 1000 transients are stored in 32K data points using a spectral window of 60 ppm (0-60ppm).
• PB-I component (A): butene-1 homopolymer having a content of fraction soluble in xylene at 0 0 C of 65% and Flexural Modulus (measured according to ISO 178) of 18.7
• PB-2 (component (A)): butene-1 /ethylene copolymer prepared as described hereinafter.
• PP (component (B)): PP Homopolymer having fraction insoluble in xylene at room temperature of 95%, a Melt flow rate 2.0 g/10 min (230°C/2.16Kg), a tensile modulus of 1500 MPa (1 mm/min) according to ISO 527-1, -2; a density of 0.900 g/cm 3 ISO 1183; a Melting Temperature of 163°C according to ISO MTM 15902.
• PB-2 butene-1 /ethylene copolymer
• the sequential polymerization was carried out in two liquid-phase stirred reactors connected in series in which liquid butene-1 constituted the liquid medium.
• the polyolefin compositions used in the examples are blends made of the above described PP homo as component (B), and from 20 to 60%wt of the above described PB copolymers as component (A), except for the composition of Reference Example 1, which is made of PP homo only.
• the blends are made using a Brabender extruder.
• the composition of the blends is reported in Table C below. Table C
• Cast films are prepared from the above described blends , using a Collin Cast film apparatus.
• the cast films are then stretched 6x6 by a TM-Long stretching machine.
• the resulting monolayer bi-oriented films have a thickness from 22 to 35 ⁇ m.

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• Chemical & Material Sciences (AREA)
• Health & Medical Sciences (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Medicinal Chemistry (AREA)
• Polymers & Plastics (AREA)
• Organic Chemistry (AREA)
• Engineering & Computer Science (AREA)
• Manufacturing & Machinery (AREA)
• Materials Engineering (AREA)
• Compositions Of Macromolecular Compounds (AREA)
• Manufacture Of Macromolecular Shaped Articles (AREA)
• Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
• Packging For Living Organisms, Food Or Medicinal Products That Are Sensitive To Environmental Conditiond (AREA)
• Packages (AREA)
• Laminated Bodies (AREA)
• Wrappers (AREA)

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